温控相转移配体及催化(ⅩⅥ)──Rh/PETPP催化的水/有机两相邻氯硝基苯CO还原反应动力学的研究  

Thermoregulated Phase-transfer Ligands and Catalysis(ⅩⅥ)──Kinetics Investigation of CO Selective Reduction of Aromatic Nitro Compounds Catalyzed by Rh/PETPP in Two-phasic System

作　　者：梅建庭[1] 蒋景阳[1] 王艳华[1] 吴小伟[1] 金子林[1] 

机构地区：[1]大连理工大学精细化工国家重点实验室

出　　处：《高等学校化学学报》2002年第5期915-918,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:29876004); 教育部博士点科研基金(批准号:98014111)资助.

摘　　要：首次将具有“温控相转移催化”功能的非离子表面活性水溶性膦／铑配合物用于以CO为还原剂的水／有机两相芳香硝基物选择还原反应．以邻氯硝基苯为底物考察了反应温度、CO压力、底物浓度、催化剂浓度和水／有机两相体积比等对反应转化率和选择性的影响．结果表明，当反应条件为 150℃和4 MPa，反应32 h时，邻氯硝基苯的转化率为 98％，邻氯苯胺的选择性接近 100％．动力学研究表明，底物浓度和催化剂浓度分别对反应速率呈一级，反应的表观活化能Ea=131．13 kJ／mol．Abstract The nonionic water-soluble phosphine ligand P[C6H4-p-(OC2H4)6OH]3(PETP)/Rh complex termed the thermoregulated phase-transfer catalysis (TRPTC) was applied to CO selective reduction of ni-troarenes compounds in the aqueous/organic two-phase. Using o-ClC6H4NO2 as a substrate, the influences of the reaction temperature, CO pressure, concentration of substrate, concentration of catalyst and volume ratio of aqueous to organic on the catalyst properties were studied. Under the conditions 423 K, pco=4 MPa and t = 32 h, the conversions of o-ClC6H4NO2 were 98% and the selectivity for the corresponding amine was higher than 99%. The kinetics investigation suggested that first-order dependence was observed for the effect of the concentration of catalyst and o-ClC6H4NO2. The apparent activation energy was 131. 13 kJ/mol.

关 键 词：温控相转移配体 水/有机两相催化 邻氯硝基苯 CO 选择还原 反应动力学 邻氯苯胺 水溶性膦/铑配合物 

分 类 号：O625.633[理学—有机化学] O643.32[理学—化学]